This work deals with a new class of vanadium pentoxide nanocomposites containing supramolecular iron or manganese tetrapyridyl porphyrins coordinated to four [Ru(bipy)2Cl]+ complexes. Their characterization was carried out by means of X-ray diffraction, SEM, AFM, confocal Raman microscopy, electronic spectroscopy and electrochemistry. According to X-ray diffraction, the original VXG lamellar framework was maintained in the nanocomposite material, but the interlamellar distance increased from 11.6 Å to 18.5 Å, reflecting the intercalation of the porphyrin species into the inorganic matrix. The films generated by direct deposition of the nanocomposite aqueous suspensions onto interdigitated gold electrodes exhibited good electrical and electrochemical performance for application in amperometric sensors.